N-(4, 5-dihydroxy-n-amyl) and n-(4, 5-diacyloxy-n-amyl) aromatic amines



Patented June 7, 1949 N- (4,5-DIHYDROXY-N -AMY L) AND N- (4,5-DI-ACYLOXY-N-AMYL) AROMATIC AMINES Joseph B. Dickey, Rochester, N.. Y.,assignor to Eastman Kodak Company, Rochester, N. Y., a corporation ofNew Jersey No Drawing. Application August 4, 1944, Serial No. 548,140

4 Claims. 1

This invention relates to aromatic amino compounds containing on theamino. nitrogen atom a 4,5-dihydroxy-n-arnyl or a 4,5-diacyloxy-namylgroup, and to a process for preparing such compounds.

N-(B-hydroxyethyl)-aniline and N-(pJ-dihydroxypropyl) -aniline are wellknown, compounds which are very useful as dye intermediates. The formerof these compounds can be prepared by condensing aniline with ethyleneoxide. The latter compound does not lend itself to preparation in asimilar manner, and is Prepared by condensing aniline with a-glycerolmonochlorohydrin in the presence of an acid-binding agent. The formercompound can also be prepared by condensing aniline with ethylenechlorohydrin, in the presence of an acid-binding agent.

I have now found that N-(4,5-dihydroxy-nai'nyl)-a1omatlc amines can beprepared by condensing i,5-diacyloxyn-amyl halides(l-halogenopentane-4,5-diol dicarboxylates) with aromatic amines, andhydrolyzing the resulting N- (4,5-diacyl.oxy-n-amyl) aromatic amine. TheN- (4,5-dihydroxy-n-amyl) -aromatic amines are especially useful ascoupling components in the formation of azo dyes (see the copendingapplication of Joseph B. Dickey and James G. Mc-

Serial No. 484,079, filed April 22, 1943, now Patent No. 2,386,599, ofwhich the instant application is a continuation-in-part). My newbydroxyalkyl compounds contain a hydroxyalkyl group having five carbonatoms and two hydroxyl groups (ratio of 5:2) and diner from. the knownN-(hydroxyalkyl) -aromatic amines which con-- tain carbon atoms andhydroxyl groups. in. the hydroxyalkyl group in a ratio not greater than2:1, in that my new compounds yield azo dyes which remain bright on thetextile after being applied to textiles made from cellulose acetaterayon yarn, whereas azo dyes containing N-hydroxyalkyl groups of equalcarbon content but having a smaller carbon atom to hydroxyi group ratiotend to become dull on the textile.

It is, accordingly, an object of my invention to provide new aminocompounds and to provide a process for the preparation thereof. Otherobjects will become apparent hereinafter.

in accordance with my invention, an aromatic amine of the primary orsecondary type, is condensed with a 4,5-diacyloxy-n-amyl halide, in

the presence of an acid-binding agent. Aromatic amines of the primary orsecondary type include aniline, m-chloroaniline, m-anisidine,o-anisidine, o-toluidine, o-chloroaniline, e-naphthylamine,,B-naphthylamine, o-aminodiphenyl, tetrahydroquinoline, benzomorpholine,o-nitroaniline, 2-methyltetrahydroquinoline,'l-methyltetrahydroquinoline, Z-methylbenzomorporline, N- methylaniline,N ethylam'line, N (p-hydroxyethyl) -aniline, N- (fl-hydroxyethyl)-m-toluidine, etc. A group of aromatic amines which give rise to veryuseful compounds in accordance with my invention can be defined by thefollowing general formula:

wherein R. rep-resents an aryl group containing not more than twocarbocyclic rings, the position in the aryl group para to the groupcontaining only a hydrogen atom, and R represents hydrogen or an alcoholradical, e. g. methyl, ,B-hydroxyethyl, ethyl, fi-ethoxyethyl,tetrahydrofurfuryl 4,5 dihydroxy n amyl, etc. Another group of amineswhich also give rise to very useful compounds in accordance with myinvention can be defined by the following general formula:

wherein D represents a monocyclic o-arylene group of the benzene series,the position in the o-arylene group para to the group containing only ahydrogen atom, J repre sents a 1,2-alkylene group and Q represents amember selected from the group consisting of methylene and oxygen. 7

The 4,5-diacyloxy-n-amyl halides employed in Example 1.-N-(p-hydroryethyl) -N- (4,5-diacetoxy-n-amyl) -m-tluidzne om-orn-orr 0 COH:

15.1 g. (0.1 mole) of N-(fi-hydroxyethyD-mtoluidine were mixed with 25g. (0.11 mole) of 4,5-diacetoxy-n-amyl chloride (l-chloropentane-4,5-diol diacetate) and 63 g. (0.6 mole) of sodium carbonate. Themixture was heated, with stirring, at 180 to 190 C. for hours in an oilbath. The mixture was cooled and diluted with 50 cc. of ethyl alcohol.The sodium chloride was filtered off. The alcohol was removed from thefiltrate by distillation and the residue was distilled under reducedpressure. The N-(B-hydroxyethyD-N- (4,5-diacetoxy-n-amyl)-m-toluidinedistilled at 238 to 241 C. at 4 mm. of mercury pressure.

Easample 2.-N- (,e-hydroxyethyl) -N- (4,5-

dihydromy-n-amg l) -m-tolm'dine CHa-CHz-OH (EH3 ()H on 5 g. of theN-(fi-hydroxyethyl)-N-(4,5-diacetoxy-n-a-myl)-m-toluidine obtained inthe foregoing example was heated with 30 cc. of per cent (by weight)aqueous sulfuric acid at 95-100 C. for about 3 hours. The mixture wasthen cooled and made alkaline with sodium hydroxide. The oil whichseparated was taken up in diethyl ether. The ether was removed from theextract by distillation and the residue distilled under reducedpressure. The N- (,B-hydroxyethyl) -N- (4,5-dihydroxy-n-amyl)-m-toluidine distilled at 245 to 250 C. at 4 mm. ofmercury pressure.

Example 3.N- (4,5-dz'acetory-n-amyl)Z-methyl-I,2,3,4-tetra-hydroquinoline 14.7 g. (0.1 mole) of2-methyi-l,2,3,4=-tetrahydroquinoline, g. (0.11 mole) of4,5-diacetoxy-n-amyl chloride (1-chloropentane-4,5-diol diacetate) and63 g. (0.6 mole) of sodium carbonate were heated together with stirringin an oil bath at 200 C. for about 5 hours. The mixture was cooled, anddiluted with cc. of ethyl alcohol. The salt (sodium chloride) wasfiltered oil. The filtrate was distilled to remove ethyl alcohol and theresidue was distilled under reduced pressure. About of the residue wasunreacted 4,5-diacetoxy-n-amyl chloride and 2-methyl-1,2,3,4-tetrahydroquinoline. The N-(4,5- diacetoxy-n amyl)-2-methyl-1,2,3,4-tetrahydroquinoline distilled over at 215 to 225 C. at9 mm. of mercury pressure. It was a very viscous liquid.

Ezrample 4.N (4,5 -dihydromy-n-amyl) Z-methyl-I,2,3,4-tetmhydroquinoline Hon,

N 3112-0 Hz-CH2--CH CH'JOH 5 g. of the N-(4,5-diacetoxy-n-amyl)-2-methyl- 123,4-tetrahydroquinoline obtained in Example 3 were heatedon a steam bath with 30 cc. of aqueous sulfuric acid (1 part by weightof acid and 6 parts of water), for 3 hours. The mixture was then madealkaline with sodium carbonate. The alkaline mixture was extracted withbenzene. The benzene extract was washed with water. The benzene was thenremoved from the extract by distillation under reduced pressure, leavingN- (4,5-dihydroxy-n-amyl) -2-methy1-1,2,3,4 tetrahydroquinoline.

10.7 g. (0.1 mole) of m-toluidine, 66 g. (0.25 mole) of4,5-diacetoxy-n-amyl bromide (l-bromopentane-fi-diol diacetate) and 126g. of sodium carbonate were heated with stirring for 6 hours at to C.The mixture was cooled and diluted with 50 cc. of ethyl alcohol. Thesalt was filtered off. The filtrate was distilled under reduced pressureand the N,N-di-(4,5-diacetoxyn-amyl) -m-toluidine distilled over at 193to 199 C. at 1.5 mm. of mercury pressure. 5 g. of this diacetoxycompound was heated with 30 cc. of 10 per cent (by weight) aqueoussulfuric acid at 95-100 C. for about 3 hours. The mixture was cooled andmade alkaline with sodium hydroxide. The alkaline mixture was extractedwith diethyl ether. The ether was distilled from the extract and theresidue was distilled under reduced pressure. N,N-di-(4,5-dihydroxy)-n-amyl m toluidine distilled at 196-202 C. at 2 mm. of mercurypressure.

In a manner similar to that illustrated in the foregoing examples thefollowing compounds were prepared:

Boiling point, C.

N-(4, sdlacetoxy-n-amyl)-a-naphthylamine 252-257/4 mm. N-(4,fi-dihydroxy-n amyll-a-uaphthylaminc 240-250/4 mm. N-(4,5-d1acetoxy-n-amyl)-2-methoxy-5-methy e zeue 220-235/4 mm. N-(4,5-d1hydroxy-n-amyl)-2-methoxy-5-methyl-bcnzene 194-198/3 mm. N -(4,5-diacctoxy-n-amhl)-N-methylaniline 222-224/15 mm.

N ethyl-N-(4, Mincetoxy-n-amyl)-anilinc. 180-205/4 mm. N-ethyl-N-( l,5-dihydroxy-n-amyl)-aniline 186-100/4 mm. N-(4, 5-d1acetoxy-n-amyl)-7methyl-l, 2, 3, 4-tctrahydroqrnnollne 215-218/4 mm. N-(4,5-d1hydroxy-n-amyl) ethyl-1, 2, 3, 4-tetrahydroquinoline 221-223/4 mm.N-(4, 5-dihy lroxy-n-nmyl)-2, 7-dimethylbenzomorpholme 223-228/1mm.N,N-d1 (4,5-d1hydroxy-n-amyl) l--amino-3- My new compounds can also beemployed in the preparation of indophenol dyes.

As acid-binding agents, not only alkali metal carbonates can be employedas illustrated in the foregoing examples, but alkaline earth metal.carbonates, alkali metal hydroxides, alkaline earth metal hydroxidesand tertiary amines can be em ployed. In hydrolyzing the 4,5-diacyloxycompounds to obtain the 4,5-dihydroxy compounds, the hydrolysis isadvantageously carriedout in the presence of a water-soluble acid.Hydrochloric' acid, phosphoric acid or chloric acid may be employedinstead of the sulfuric acidfill ustrated in the foregoing examples.Alkaline 'hydroiysis can also be employed to convert the diacyloxycompounds to the dihydroxy compounds- What I claimas my invention anddesire to be secured by Letters Patent of the United States is:

1. The amines which are represented by the following general formula:

Q D/ \J cm-om-onron-omon wherein D represents a monocyclic o-arylenegroup of the benzene series, the carbon atom in the aryl group in thepara position to the group having only a hydrogen atom attached thereto,J represents a 1,2-alkylene group and Q represents a member selectedfrom the group consisting of a methylene group and an oxygen atom. 2.The amines which are represented by the following general formula:

(JHr-CHrCHrCH-CHaOH angers wherein D represents a monocyclic o-arylenegroup of the benzene series, the carbon atom in the aryl group in thepara position to the om-om-om-en-omoo group having only a hydrogen atomattached thereto.

3. The amines which are represented by the following general formula:

I onr-om-cm-cn omon wherein J represents a 1,2-alkylene group.

4. N- (4,5-dihydroxy-n-amyl) -2-methy1-1,2,3,4- tetrahydroquinoline.

JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,735,961 Dreyfus Nov. 19, 19292,190,133v Epstein Feb. 13, 1940 OTHER REFERENCES Chemical Abstracts,vol. 33, page 6259 (1939) ibid., vol. 36, page 751 (1942).

Beilstein: Handbuch der Organischem Chemie, (4th ed.), vol. 12, page 183(1929).

Karrer: Organic Chemistry (Nordemann Publishing Co., New York; 1938)pages '71 and 72.

Compt. rend., vol. 211, page 645 (1940).

